NATIONAL WATER-QUALITY ASSESSMENT PROGRAM Pesticide Compounds in Streamwater in the Delaware River Basin, December 1998–August 2001 Scientific Investigations Report 2004-5105 U.S. Department of the Interior U.S. Geological Survey NATIONAL WATER-QUALITY ASSESSMENT PROGRAM Pesticide Compounds in Streamwater in the Delaware River Basin, December 1998–August 2001 Scientific Investigations Report 2004-5105 U.S. Department of the Interior U.S. Geological Survey Pesticide Compounds in Streamwater in the Delaware River Basin, December 1998–August 2001 By R. Edward Hickman Prepared as part of the NATIONAL WATER-QUALITY ASSESSMENT PROGRAM Scientific Investigations Report 2004-5105 U.S. Department of the Interior U.S. Geological Survey U.S. Department of the Interior Gale A. Norton, Secretary U.S. Geological Survey Charles G. Groat, Director U.S. Geological Survey, Reston, Virginia: 2004 For sale by U.S. Geological Survey, Information Services Box 25286, Denver Federal Center Denver, CO 80225 For additional information write to: District Chief U.S. Geological Survey Mountain View Office Park 810 Bear Tavern Road West Trenton, NJ 08628 For more information about the USGS and its products: Telephone: 1-888-ASK-USGS World Wide Web: http://www.usgs.gov/ Any use of trade, product, or firm names in this publication is for descriptive purposes only and does not imply endorsement by the U.S. Government. Although this report is in the public domain, permission must be secured from the individual copyright owners to reproduce any copyrighted materials contained within this report. iii Foreword The U.S. Geological Survey (USGS) is committed to serve the Nation with accurate and timely sci- entific information that helps enhance and protect the overall quality of life, and facilitates effec- tive management of water, biological, energy, and mineral resources. (http://www.usgs.gov/). Information on the quality of the Nation’s water resources is of critical interest to the USGS because it is so integrally linked to the long-term availability of water that is clean and safe for drinking and recreation and that is suitable for industry, irrigation, and habitat for fish and wildlife. Escalating population growth and increasing demands for the multiple water uses make water availability, now measured in terms of quantity and quality, even more critical to the long-term sustainability of our communities and ecosystems. The USGS implemented the National Water-Quality Assessment (NAWQA) Program to support national, regional, and local information needs and decisions related to water-quality manage- ment and policy. (http://water.usgs.gov/nawqa/). Shaped by and coordinated with ongoing efforts of other Federal, State, and local agencies, the NAWQA Program is designed to answer: What is the condition of our Nation’s streams and ground water? How are the conditions changing over time? How do natural features and human activities affect the quality of streams and ground water, and where are those effects most pronounced? By combining information on water chem- istry, physical characteristics, stream habitat, and aquatic life, the NAWQA Program aims to pro- vide science-based insights for current and emerging water issues and priorities. NAWQA results can contribute to informed decisions that result in practical and effective water-resource manage- ment and strategies that protect and restore water quality. Since 1991, the NAWQA Program has implemented interdisciplinary assessments in more than 50 of the Nation’s most important river basins and aquifers, referred to as Study Units. (http://water.usgs.gov/nawqa/nawqamap.html). Collectively, these Study Units account for more than 60 percent of the overall water use and population served by public water supply, and are representative of the Nation’s major hydrologic landscapes, priority ecological resources, and agricultural, urban, and natural sources of contamination. Each assessment is guided by a nationally consistent study design and methods of sampling and analysis. The assessments thereby build local knowledge about water-quality issues and trends in a particular stream or aquifer while providing an understanding of how and why water quality varies regionally and nationally. The consistent, multi-scale approach helps to determine if certain types of water-quality issues are isolated or pervasive, and allows direct comparisons of how human activities and natural processes affect water quality and ecological health in the Nation’s diverse geographic and environmental settings. Comprehensive assessments on pesticides, nutrients, volatile organic compounds, trace metals, and aquatic ecology are developed at the national scale through comparative analysis of the Study-Unit findings. (http://water.usgs.gov/nawqa/natsyn.html). The USGS places high value on the communication and dissemination of credible, timely, and rel- evant science so that the most recent and available knowledge about water resources can be applied in management and policy decisions. We hope this NAWQA publication will provide you the needed insights and information to meet your needs, and thereby foster increased awareness and involvement in the protection and restoration of our Nation’s waters. iv The NAWQA Program recognizes that a national assessment by a single program cannot address all water-resource issues of interest. External coordination at all levels is critical for a fully inte- grated understanding of watersheds and for cost-effective management, regulation, and conser- vation of our Nation’s water resources. The Program, therefore, depends extensively on the advice, cooperation, and information from other Federal, State, interstate, Tribal, and local agen- cies, non-government organizations, industry, academia, and other stakeholder groups. The assis- tance and suggestions of all are greatly appreciated. Robert M. Hirsch Associate Director for Water v Contents Abstract . 1 Introduction . 1 Purpose and Scope . 2 Description of the Study Area . 2 Design and Methods of Study . 2 Streamwater Sampling Sites . 5 Field Methods . 5 Laboratory Methods . 11 Quality Assurance/Quality Control Methods . 11 Application Rates of Pesticides to Agricultural Land . 11 Methods of Data Analysis . 14 Pesticide Compounds in Streamwater in the Delaware River Basin . 14 Summary of Detection Frequencies and Concentrations . 14 Pesticide Compounds (Gas Chromatography) . 14 Pesticide Degradation Products (High Performance Liquid Chromatography) . 17 Bias and Variability of Detection Frequencies and Concentrations . 17 Pesticide Compounds (Gas Chromatography) . 17 Pesticide Degradation Products (High Performance Liquid Chromatography) . 18 Relations Between Concentrations of Selected Pesticides and Indicators of Agricultural and Nonagricultural Uses of Pesticides . 18 Variation in Concentrations of Selected Pesticides with Season . 26 Relations of Concentrations of Selected Pesticides to Streamwater Turbidity . 26 Comparison of Concentrations of Selected Degradation Products with Concentrations of Parent Pesticides . 29 Deethylatrazine . 29 Ethane Sulfonic Acid and Oxanilic Acid Degradation Products of Alachlor, Acetochlor, and Metolachlor at Two Sites . 30 Comparison of Concentrations of Pesticide Compounds to Standards and Guidelines for the Protection of Human Health and Aquatic Life . 31 Human Health . 31 Aquatic Life . 33 Summary and Conclusions . 33 References Cited . 34 vi Figures 1–2. Maps showing— 1. Location of the Delaware River Basin, New York, Pennsylvania, New Jersey, and Delaware . .3 2. Physiographic provinces and land use in the Delaware River Basin, 1992 . .4 3. Graph showing crops with the largest areas of cultivation in the Delaware River Basin. .5 4–5. Maps showing— 4. Location of fixed streamwater sampling sites with drainage areas in the Delaware River Basin . .6 5. Location of synoptic and fixed streamwater sampling sites in the Delaware River Basin, 1998–2001. 10 6–8. Graphs showing— 6. Frequences of detection of the pesticide compounds most often detected in 531 samples of streamwater by use of gas chromatography, Delaware River Basin, December 1998–August 2001. 17 7. Relation of frequency of detection to estimated annual application to agricultural land within the Delaware River Basin. 19 8. Relation of concentration of atrazine in streamwater to percentage of agricultural land in subbasins of the Delaware River Basin, May and June 2000. 20 9. Map showing streamwater sampling sites and association of atrazine under base-flow conditions, and application rates, Delaware River Basin, May and June 1999–2001 . 22 10. Graph showing relation of concentrations of prometon in streamwater to the percentage of urban land in subbasins of the Delaware River Basin, May and June 2000. 23 11. Map showing streamwater sampling sites and associated concentrations of prometon under base-flow conditions, and population density, Delaware River Basin, May and June 1999–2001. ..